Novel organophosphorus compounds based on anthracenetriol

ABSTRACT

The subject matter of the present invention is a plurality of products and the use thereof as a catalytically active composition in a method for producing aldehydes.

The present invention relates to bis- and trisphosphites containing atleast one structural element based on anthracenetriol and also to metalcomplexes thereof, to the preparation, and also to the use of the bis-and trisphosphites as multidentate compounds in catalytic reactions.

The reactions between olefin compounds, carbon monoxide and hydrogen inthe presence of a catalyst to form the aldehydes having one carbon atommore is known as hydroformylation (oxo synthesis). Catalysts used inthese reactions are frequently compounds of the transition metals ofgroup VIII of the periodic table, especially compounds of rhodium and ofcobalt. Hydroformylation using rhodium compounds generally offers theadvantage of higher selectivity compared with catalysis using cobalt andleads to products having a higher added value. Rhodium-catalyzedhydroformylation usually employs compositions that consist of rhodiumand preferably of trivalent phosphorus compounds as ligands. Knownligands are for example compounds from the classes of phosphines,phosphites and phosphonites each comprising trivalent phosphorusP^(III). Hydroformylation of olefins is reviewed in B. CORNILS, W. A.HERRMANN, “Applied Homogeneous Catalysis with Organometallic Compounds”,Vol. 1 & 2, VCH, Weinheim, N.Y., 1996.

Every catalytically active composition—based on cobalt or rhodium—hasits specific merits. Different catalytically active compositions aretherefore used depending on the feedstock and the target product, as isshown by the following examples: With rhodium and triphenylphosphine,α-olefins can be hydroformylated at comparatively low pressures.Triphenyl-phosphine as phosphorus-containing ligand is generally used inexcess, while a high ligand/rhodium ratio is required to increase theselectivity of the reaction leading to the commercially desiredn-aldehyde product.

The patents U.S. Pat. No. 4,694,109 and U.S. Pat. No. 4,879,416 describebisphosphine ligands and their use in the hydroformylation of olefins atlow syngas pressures. Ligands of this type provide high activities andhigh n/i selectivities in the hydroformylation of propene in particular.WO 95/30680 discloses bidentate phosphine ligands and their use incatalysis including inter alia in hydroformylation reactions.Ferrocene-bridged bisphosphines are described for example in the patentsU.S. Pat. No. 4,169,861, U.S. Pat. No. 4,201,714 and U.S. Pat. No.4,193,943 as ligands for hydroformylations.

The disadvantage of bi- and polydentate phosphine ligands is theirrelatively costly and inconvenient method of making. Therefore, it isoften not economically viable to use such systems in commercialprocesses. There is also the comparatively low reactivity, which has tobe technically compensated by high residence times. This in turn leadsto undesired secondary reactions for the products.

Rhodium-monophosphite complexes in catalytically active compositions areuseful for the hydroformylation of branched olefins having internaldouble bonds, but selectivity is low in respect of terminallyhydroformylated compounds. EP 0 155 508 discloses the use ofbisarylene-substituted monophosphites in the rhodium-catalyzedhydroformylation of sterically hindered olefins, e.g. isobutene.

Catalytically active compositions based on rhodium-bisphosphitecomplexes are useful for the hydroformylation of linear olefins havingterminal and internal double bonds to give predominantly terminallyhydroformylated products. By contrast, branched olefins having internaldouble bonds are only converted to a minor extent. These phosphitescoordinate onto a transition metal centre to provide catalysts ofenhanced activity, but the on-stream life of these catalytically activecompositions is unsatisfactory, inter alia because of the phosphiteligands' sensitivity to hydrolysis. The use of substituted bisaryl diolsas starting materials for the phosphite ligands, as described in EP 0214 622 or EP 0 472 071, wrought appreciable improvements.

The literature says that the catalytically active compositions of theseligands based on rhodium are extremely active in the hydroformylation ofα-olefins. The patents U.S. Pat. No. 4,668,651, U.S. Pat. No. 4,748,261and U.S. Pat. No. 4,885,401 describe polyphosphite ligands with whichα-olefins but also 2-butene can be converted to the terminallyhydroformylated products with high selectivity. Bidentate ligands ofthis type have also been used for hydroformylating butadiene (U.S. Pat.No. 5,312,996).

The bisphosphites disclosed in EP 1 294 731, when used in thehydroformylation of octene mixtures, provide olefin conversions of up to98%. However, the likewise desired n-selectivity to nonanal at 36.8% toat most 57.6% is in need of improvement. This applies all the morebecause the use of a catalytically active composition in commercialprocesses requires an on-stream life of days rather than hours.

Although the bisphosphites mentioned are good ligands for rhodium-basedhydroformylation catalysts, it is desirable to develop novel ligands.

These novel ligands shall:

-   -   have high n-selectivities in the hydroformylation of olefins or        olefin-containing mixtures with internal double bonds, i.e.        isomerizing properties;    -   also possess an improved resistance to inherent catalyst        poisons, such as water for example, and thus provide prolonged        on-stream life when used in a catalytically active composition        for hydroformylation;    -   and also reduce the known clustering tendency of rhodium in        catalytically active compositions and thereby again provide        prolonged on-stream life when used in a catalytically active        composition for hydroformylation.

This object is achieved by a compound according to the present inventioncomprising the structural element (I):

and

-   -   the compound comprises at least two O—P^(III) bonds, wherein        these may emanate from the same P^(III) or from different        P^(III)s;    -   in the event that the structural element (I) occurs twice in the        compound, these are connected to each other by a C10-C10′ carbon        bond or via the following X¹-G¹-X² unit:

—X¹-G¹-X²—

where X¹ is connected to a P^(III) of the first structural element (I)and X² to a P^(III) of the second structural element (I),with G¹=a linear or branched, aliphatic or aromatic or heteroaromatic orfused aromatic or fused aromatic-heteroaromatic hydrocarbon group withany desired further substitution;wherein X¹, X² is selected from: O, NY¹, CY²Y³;wherein the meaning may have been chosen for X¹ and X² independently ofeach other;wherein Y¹, Y², Y³ is selected from: hydrogen, substituted orunsubstituted aliphatic, substituted or unsubstituted aromatichydrocarbon group;wherein the meaning may have been chosen for each Y¹ to Y³ independentlyof each other;wherein two or more of Y¹ to Y³ may be linked to each other covalently;wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷ are selected from: hydrogen,substituted or unsubstituted, linear or branched, aliphatic or aromatichydrocarbon group; F, Cl, Br, I, —OR⁸, —C(O)R⁹, —CO₂R¹⁰, —CO₂M¹, —SR¹¹,—SOR¹², —SO₂R¹³, —SO₃R¹⁴, —SO₃M², —NR¹⁵R¹⁶;wherein R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶ are selected from:hydrogen, substituted or unsubstituted, linear or branched, aliphatic oraromatic or heteroaromatic or fused aromatic or fusedaromatic-heteroaromatic hydrocarbon group; —OR¹⁷;wherein R¹⁷ is selected from: hydrogen, unsubstituted or substituted,linear or branched, aliphatic or aromatic hydrocarbon group; wherein twoor more of R¹ to R¹⁷ may be linked to each other covalently;wherein M¹ and M² are selected from: alkali metal, alkaline earth metal,ammonium, phosphonium, andwherein the meaning may have been chosen for M¹ and M² independently ofeach other.

In an embodiment of the invention, the compound comprises the structuralelement (II):

wherein W is selected from:

-   -   hydrogen;    -   aliphatic, aromatic, heteroaromatic, fused aromatic, fused        aromatic-heteroaromatic hydrocarbon group with any desired        further substitution;    -   a P^(III)(G²)(G³) group:

wherein G² and G³ are each selected from: hydrogen; linear or branched,aliphatic or aromatic or heteroaromatic or fused aromatic or fusedaromatic-heteroaromatic hydrocarbon group with any desired furthersubstitution; F, Cl, Br, I, or —OR¹⁸, —C(O)R¹⁹, —CO₂R²⁰, —CO₂M¹, —SR²¹,SOR²², —SO₂R²³, —SO₃R²⁴, —SO₃M², —NR²⁵R²⁶;wherein R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶ are selected from:hydrogen, substituted or unsubstituted, linear or branched, aliphatic oraromatic hydrocarbon group; —OR²⁷; wherein R²⁷ is selected from:hydrogen, substituted or unsubstituted, linear or branched, aliphatic oraromatic hydrocarbon group; F, Cl, Br, I;wherein M¹ and M² are selected from: alkali metal, alkaline earth metal,ammonium, phosphonium, andwherein the meaning may have been chosen for M¹ and M² independently ofeach other,wherein the meaning may have been chosen for G² and G³ independently ofeach other, and G² and G³ may be linked to each other covalently,—SiR²⁸R²⁹R³⁰; with R²⁸, R²⁹, R³⁰=hydrogen; linear or branched, aliphaticor aromatic or heteroaromatic or fused aromatic or fusedaromatic-heteroaromatic hydrocarbon group with any desired furthersubstitution; wherein the meaning may have been chosen for R²⁸, R²⁹ andR³⁰ independently of each other and wherein R²⁸ and R²⁹ may be linked toeach other covalently.

In an embodiment of the invention, the compound comprises the structuralelement (III):

wherein Z represents G⁴ or an X¹-G¹-X² unit,and G⁴ is selected from: hydrogen; linear or branched, aliphatic oraromatic or heteroaromatic or fused aromatic or fusedaromatic-heteroaromatic hydrocarbon group with any desired furthersubstitution; F, Cl, Br, I, or —OR³¹, —C(O)R³², —CO₂R³³, —CO₂M¹, —SR³⁴,—SOR³⁵, —SO₂R³⁶, —SO₃R³⁷, —SO₃M², —NR³⁸R³⁹,wherein R³¹, R³², R³³, R³⁴, R³⁵, R³⁶, R³⁷, R³⁸, R³⁹ are selected from:hydrogen, substituted or unsubstituted, linear or branched, aliphatic oraromatic hydrocarbon group; —OR⁴⁰;wherein R⁴⁰ is selected from: hydrogen, substituted or unsubstituted,linear or branched, aliphatic or aromatic hydrocarbon group;wherein M¹ and M² are selected from: alkali metal, alkaline earth metal,ammonium, phosphonium, andwherein the meaning may have been chosen for M¹ and M² independently ofeach other.

In an embodiment of the invention, the compound comprises the structuralelement (IV):

wherein G⁵ and G⁶ are selected from: hydrogen; linear or branched;aliphatic or aromatic or heteroaromatic or fused aromatic or fusedaromatic-heteroaromatic hydrocarbon group with any desired furthersubstitution; F, Cl, Br, I, or —OR⁴¹, —C(O)R⁴², —CO₂R⁴³, —CO₂M¹, —SR⁴⁴,—SOR⁴⁵, —SO₂R⁴⁶, —SO₃R⁴⁷, —SO₃M², —NR⁴⁸R⁴⁹,wherein R⁴¹, R⁴², R⁴³, R⁴⁴, R⁴⁵, R⁴⁶, R⁴⁷, R⁴⁸, R⁴⁹ are selected from:hydrogen, substituted or unsubstituted, linear or branched, aliphatic oraromatic hydrocarbon group; —OR⁵⁰;wherein R⁵⁰ is selected from: hydrogen, substituted or unsubstituted,linear or branched, aliphatic or aromatic hydrocarbon group;wherein M¹ and M² are selected from: alkali metal, alkaline earth metal,ammonium, phosphonium, andwherein the meaning may have been chosen for M¹ and M² independently ofeach other,wherein the meaning may have been chosen for G⁵ and G⁶ independently ofeach other, and G⁵ and G⁶ may be linked to each other covalently.

In an embodiment of the invention, W represents a P^(III)(G²)(G³) group.

In an embodiment of the invention, G², G³ is =—OR¹⁸.

In an embodiment of the invention, G⁵, G⁶ is =—OR⁴¹.

In an embodiment of the invention, X¹, X² is =O.

In an embodiment of the invention, G¹ comprises a bisarylene grouphaving any desired further substitution.

In an embodiment of the invention, G¹ comprises the structural element(V):

-   -   with R⁵¹, R⁵², R⁵³, R⁵⁴, R⁵⁵, R⁵⁶, R⁵⁷, R⁵⁸=hydrogen; linear or        branched, aliphatic or aromatic or heteroaromatic or fused        aromatic or fused aromatic-heteroaromatic hydrocarbon group with        any desired further substitution; F, Cl, Br, or I; or —OR⁵⁹,        —COR⁶⁰, —CO₂R⁶¹, —CO₂M¹, —SR⁶², —SOR⁶³, —SO₂R⁶⁴, —SO₃R⁶⁵,        —SO₃M², —NR⁶⁶R⁶⁷, or N═CR⁶⁸R⁶⁹; wherein the meaning may have        been chosen independently for each R⁵¹ to R⁵⁸ independently of        each other and wherein two or more of R⁵¹ to R⁵⁸ may be linked        to each other covalently;    -   wherein R⁵⁹, R⁶⁰, R⁶¹, R⁶², R⁶³, R⁶⁴, R⁶⁵, R⁶⁶, R⁶⁷ are selected        from: hydrogen, substituted or unsubstituted, linear or        branched, aliphatic or aromatic hydrocarbon group; —OR⁶⁸;    -   wherein R⁶⁸ is selected from: hydrogen, substituted or        unsubstituted, linear or branched, aliphatic or aromatic        hydrocarbon group;    -   wherein M¹ and M² are selected from: alkali metal, alkaline        earth metal, ammonium, phosphonium, and    -   wherein the meaning may have been chosen for M¹ and M²        independently of each other,    -   and with a and b as attachment points to X¹ and X².

In an embodiment of the invention, G² and G³ are linked to each othercovalently.

In an embodiment of the invention, the link G²-G³ comprises thefollowing structural element (VI):

with R⁶⁹, R⁷⁰, R⁷¹, R⁷², R⁷³, R⁷⁴, R⁷⁵, R⁷⁶=hydrogen; linear orbranched, aliphatic or aromatic or heteroaromatic or fused aromatic orfused aromatic-heteroaromatic hydrocarbon group with any desired furthersubstitution; F, Cl, Br, or I; or —OR⁷⁷, —COR⁷⁸, —CO₂R⁷⁹, —CO₂M¹, —SR⁸⁰,—SOR⁸¹, —SO₂R⁸², —SO₃R⁸³, —SO₃M², —NR⁸⁴R⁸⁵, or N═CR⁸⁶R⁸⁷; wherein themeaning may have been chosen for each R⁶⁹ to R⁷⁶ independently of eachother and wherein two or more of R⁶⁹ to R⁷⁶ may be linked to each othercovalently;wherein R⁷⁷, R⁷⁸, R⁷⁹, R⁸⁰, R⁸¹, R⁸², R⁸³, R⁸⁴, R⁸⁵ are selected from:hydrogen, substituted or unsubstituted, linear or branched, aliphatic oraromatic hydrocarbon group; —OR⁸⁶;wherein R⁸⁶ is selected from: hydrogen, substituted or unsubstituted,linear or branched, aliphatic or aromatic hydrocarbon group;wherein M¹ and M² are selected from: alkali metal, alkaline earth metal,ammonium, phosphonium, andwherein the meaning may have been chosen for M¹ and M² independently ofeach other.

In an embodiment of the invention, G⁵ and G⁶ are linked to each othercovalently.

In an embodiment of the invention, the link G⁵-G⁶ comprises thefollowing structural element (VII):

with R⁸⁷, R⁸⁸, R⁸⁹, R⁹⁰, R⁹¹, R⁹², R⁹³, R⁹⁴=hydrogen; linear orbranched, aliphatic or aromatic or heteroaromatic or fused aromatic orfused aromatic-heteroaromatic hydrocarbon group with any desired furthersubstitution; F, Cl, Br, or I; or —OR⁹⁵, —COR⁹⁶, —CO₂R⁹⁷, —CO₂M¹, —SR⁹⁸,—SOR⁹⁹, —SO₂R¹⁰⁰, —SO₃R¹⁰¹, —SO₃M², —NR¹⁰²R¹⁰³, or N═CR¹⁰⁴R¹⁰⁵; whereinthe meaning may have been chosen for each R³¹ to R³⁸ independently ofeach other and wherein two or more of R⁸⁶ to R⁹³ may be linked to eachother covalently;wherein R⁹⁵, R⁹⁶, R⁹⁷, R⁹⁸, R⁹⁹, R¹⁰⁰, R¹⁰¹, R¹⁰², R¹⁰³ are selectedfrom: hydrogen, substituted or unsubstituted, linear or branched,aliphatic or aromatic hydrocarbon group; —OR¹⁰⁴;wherein R¹⁰⁴ is selected from: hydrogen, substituted or unsubstituted,linear or branched, aliphatic or aromatic hydrocarbon group; wherein M¹and M² are selected from: alkali metal, alkaline earth metal, ammonium,phosphonium, andwherein the meaning may have been chosen for M¹ and M² independently ofeach other.

In an embodiment of the invention, the P^(III)(G²)(G³) group correspondsin terms of structural formula to the P^(III)(G⁵)(G⁶) group.

In addition to the compound per se, complexes comprising such a compoundare also claimed.

In an embodiment of the invention, the complex comprises a compound asdescribed above and at least one central metal atom, wherein thecompound is coordinated onto the central metal atom via at least oneP^(III).

In an embodiment of the invention, the central metal atom is selectedfrom groups 8 to 10 of the periodic table of the elements.

In a preferred embodiment of the invention, the central metal atom isrhodium.

In addition to the complex itself, a composition comprising such acomplex is also claimed.

In an embodiment, the composition contains a compound as described abovewhich is not coordinated onto a central metal atom, and a complex asdescribed above.

In addition to the composition, use thereof is also claimed.

In an embodiment, the composition is used as catalytically activecomposition in the synthesis of organic compounds.

In an embodiment, the composition is used as a catalytically activecomposition in a process for hydroformylation of olefinicallyunsaturated hydrocarbon mixtures.

A multiphasic reaction mixture is also claimed.

In an embodiment, the multiphasic reaction mixture contains anolefinically unsaturated hydrocarbon mixture, a gas mixture containingcarbon monoxide and hydrogen, aldehydes, a composition as describedabove as catalytically active composition.

A process for hydroformylation of olefinically unsaturated hydrocarbonmixtures to aldehydes is also claimed.

In one version, this process comprises the steps of:

-   a) providing a mixture of olefinically unsaturated hydrocarbons;-   b) adding a catalytically active composition as described above;-   c) introducing a mixture comprising carbon monoxide and hydrogen;-   d) heating the reaction mixture to a temperature in the range from    80 to 120° C.;-   e) building a pressure in the range from 1.0 to 6.4 MPa;-   f) removing the olefinically unsaturated hydrocarbon mixture on    concluding the reaction.

In one version of the process, this process comprises as an additionalstep:

-   g) removing and returning unconverted olefinically unsaturated    hydrocarbon mixture into step a).

In one version of the process, this process comprises as additionalstep:

-   h) removing and returning the catalytically active composition    described to step b).

In one version of the process, this process comprises as additionalstep:

-   i) removing and returning the unconverted gas mixture containing    carbon monoxide and hydrogen into step c).

Illustrative embodiments of compounds according to the present inventionwill now be shown: Illustrative embodiments of bidentate compoundsaccording to the present invention with two phosphorus atoms:

Illustrative embodiments of tridentate compounds according to thepresent invention with three phosphorus atoms:

Illustrative embodiments of quatrodentate compounds according to thepresent invention with four phosphorous atoms:

SYNTHESIS PROTOCOLS OF SELECTED COMPOUNDS Compound 1

A suspension of 1,8,9-anthracenetriol (0.3549 g, 1.5686 mmol) in toluene(6 ml) is admixed at 0° C., under agitation, with triethylamine (0.69ml, 4.939 mmol) and then dropwise with a solution of4,8-di-tert-butyl-6-chloro-2,10-dimethoxydibenzo[d,f][1,3,2]dioxa-phosphepine(1.3267 g, 3.1372 mmol) in toluene (15 ml). The mixture is stirredovernight and filtered and the filtrate is concentrated to dryness invacuo. The residue is dried at 40° C. at 0.1 KPa for 2 h and purified bycolumn chromatography (mobile phase dichloromethane, R_(f)=0.62). Yield:1.39 g (1.39 mmol; 89%). Elemental analysis (calc. forC₅₈H₆₄O₁₁P₂=999.08 g/mol): C, 70.17 (69.73); H, 6.50 (6.46); P, 6.07(6.20) %. ¹H NMR (CD₂Cl₂): δ 0.95-1.59 (36H), 3.76-3.88 (8 signals,12H); 4.68-5.27 (1H); 6.24-8.00 (15H). Diastereomer ratio=1:5. CI-MS:(isobutane, pos.) m/e 1055 (18%, M⁺+i-C₄H₈), 999 (63%, M⁺).

Compound 2

A suspension of 1,8,9-anthracenetriol (1.076 g, 4.755 mmol) in toluene(18 ml) is admixed at 0° C. under agitation with triethylamine (2.09 ml,14.973 mmol) and then dropwise with a solution of2,4,8,10-tetra-tert-butyl-6-chlorodibenzo[d,f][1,3,2]dioxaphosphepine(4.518 g, 9.511 mmol) in toluene (45 ml). The mixture is stirredovernight at room temperature and for an additional 2 h at 70° C.,filtered and the filtrate is concentrated to dryness in vacuo. Theresidue is prepurified by column chromatography (mobilephase/hexane/dichloromethane=1:2, R_(f)=0.72) and gives a crude yield of4.27 g (3.869 mmol, 81%). Pure material is obtained by recrystallizationof hot acetonitrile. Elemental analysis (calc. for C₇₀H₈₈O₇P₂=1103.41g/mol): C, 76.00 (76.20); H, 7.86 (8.04); P, 5.41 (5.61) %. ¹H NMR(CD₂Cl₂): δ 0.80-1.45 (72H), 4.62-5.13 (1H), 5.69-7.84 (15H) ppm. CI-MS(isobutane, pos.: m/e 1103 (100%, M⁺).

Compound 3

A suspension of anthracenetriol (0.629 g, 2.782 mmol) in toluene (14 ml)is admixed at 0° C. under agitation with triethylamine (0.866 g, 8.76mmol) and then dropwise with a solution of4,8-di-tert-butyl-2,6,10-trichlorodibenzo[d,f][1,3,2]dioxaphosphepine(2.611 g, 5.563 mmol) in toluene (26 ml). The mixture is stirredovernight and filtered and the filtrate is concentrated to dryness invacuo. Recrystallization of hexane (65 ml) gives an enriched product(about 85%), which was used for further synthesis. Yield: 1.479 g (1.455mmol; 52%). ³¹P NMR (CD₂Cl₂): δ 102.8 (s, br), 105.5 (s, br), 136.5 (s,br), 138.3 (s, br) ppm.

Compound 4

Under agitation, a solution of 1,8,9-anthracenetriol (0.207 g, 0.928mmol) and triethylamine (0.294 g, 2.92 mmol) in toluene (10 ml) isadmixed at −20° C. with a solution of compound 24 (0.882 g, 0.928 mmol)in toluene (10 ml) which is added dropwise. After stirring overnight atroom temperature, the reaction solution is filtered and the filtrate isconcentrated to dryness in vacuo. The solid material obtained is driedat 50° C./0.1 KPa for 2 h and recrystallized from acetonitrile (100 ml).Yield: 0.391 g (0.411 mmol, 44%). Elemental analysis (calc. forC₇₀H₈₈O₇P₂=1103.40 g/mol): C, 75.16 (76.20); H, 8.25 (8.04); P, 5.43(5.61) %. ³¹P NMR (CD₂Cl₂): δ □ 102.8 (s, br), 109.8 (s, br), 142.2 (s,br), 142.7 (d, J_(PP)=6 Hz) ppm. By NMR spectroscopy there are twodiastereomeric products. EI-MS: m/e 1102 (5%, M⁺).

Compound 5

A solution of 1,8,9-anthracenetriol (0.538 g; 2.378 mmol) andtriethylamine (0.757 g, 7.49 mmol) in toluene (20 ml) is admixed at −20°C. under agitation with a solution of 21 (2.011 g, 2.378 mmol) intoluene (30 ml) which is added dropwise. After stirring overnight atroom temperature, the reaction solution is filtered and the filtrate isconcentrated to dryness in vacuo. The solid material obtained is driedat 50° C./0.1 KPa for 2 h and purified using column chromatography(eluent: dichloromethane, R_(f)=0.46 and 0.51, two diastereoisomers).Yield: 1.263 g (1.264 mmol; 53%). Elemental analysis (calc. forC₅₈H₆₄O₁₁P₂=999.08 g/mol): C, 68.96 (69.73); H, 6.28 (6.46); P, 6.17(6.20) %. ³¹P NMR (CD₂Cl₂): δ 104.3 (d, J_(PP)=37 Hz); 108.5 (d,J_(PP)=37 Hz), 138.4 (s, br); 140.5 (s, br) ppm. EI-MS: m/e 998 (2%,M⁺).

Compound 6

A solution of 5 (0.994 g, 0.995 mmol) in THF (7 ml) is admixed withhexamethyldisilazane (0.802 g, 4.98 mmol), dissolved in THF (12 ml). Thereaction solution is refluxed for 10 h and then concentrated to drynessin vacuo. The solid material obtained is dried at 50° C./0.1 KPa for 2h. The residue is recrystallized from hexane. Yield: 0.877 g (0.819mmol, 82%). ¹H NMR (CD₂Cl₂): δ 0.15-1.31 (45H), 3.62-3.81 (12H),6.17-7.94 (m, 15H) ppm.

Compound 7

A solution of 1 (0.966 g, 0.967 mmol) in toluene (12 ml) is admixed atroom temperature under agitation with triethylamine (0.42 ml, 3.035mmol) and then at 0° C. with a solution of2-chloro-4H-benzo[d][1,3,2]dioxaphosphinin-4-one (0.196 g, 0.967 mmol)in toluene (4 ml). The reaction mixture is warmed to room temperature,stirred overnight and filtered. The filtrate is concentrated to drynessin vacuo, and the residue is dried at 40° C./0.1 KPa for 3 h and thenpurified by column chromatography (mobile phase hexane/dichloromethane,1:10, R_(f)=0.8). Yield: 1.095 g (0.939 mmol, 97%). Elemental analysis(calc. for C₆₅H₆₇O₁₄P₃=1165.15 g/mol): C, 67.50 (67.01); H, 5.80 (5.80);P, 8.04 (7.97) %. ¹H NMR (CD₂Cl₂): δ □ 1.08-1.65 (36H), 3.68-3.94 (12H),6.10-8.10 (19H) ppm. ESI-TOF HRMS (MeOH/0.1% HCOOH in H₂O 90:10) m/e1187.3633 (100%, M+Na)⁺.

Compound 8

A solution of 1 (2.0 g, 2.002 mmol) in toluene (20 ml) is admixed atroom temperature under agitation with triethylamine (0.88 ml, 6.314mmol) and then at 0° C. with a solution of2-chloro-4H-naphtho[1,2-d][1,3,2]dioxaphosphinin-4-one (0.656 mg, 2.602mmol) in toluene (7 ml). The reaction mixture is warmed to roomtemperature, stirred overnight and filtered. The filtrate isconcentrated to dryness in vacuo, and the residue is dried at 50° C./0.1KPa for 1 h and then purified by column chromatography (mobile phasehexane/dichloromethane, 1:10, R_(f)=0.62). Yield: 2.07 g (1.703 mmol,85%). Elemental analysis (calc. for C₆₉H₆₉O₁₄P₃=1215.21 g/mol): C, 68.05(68.20); H, 5.85 (5.72); P, 7.27 (7.65) %. ¹H NMR (CD₂Cl₂): δ 1.09-1.65(36H), 3.66-3.96 (12H), 6.11-8.24 (21H) ppm. CI-MS (isobutane, pos.):m/e 1214 (1%, M⁺), 1044.

Compound 9

A solution of 2 (1.329 g, 1.204 mmol) in toluene (15 ml) is admixed atroom temperature under agitation with triethylamine (0.53 ml, 3.781mmol) and then at 0° C. with a solution of2-chloro-4H-benzo[d][1,3,2]dioxaphosphinin-4-one (0.243 mg, 1.204 mmol)in toluene (5 ml). The reaction mixture is warmed to room temperature,stirred for 48 h and filtered. The filtrate is concentrated to drynessin vacuo, and the residue is dried at 50° C./0.1 KPa for 1 h and thenpurified by column chromatography (mobile phase hexane/dichloromethane,2:1, R_(f)=0.22). Yield: 1.14 g (0.898 mmol, 74%). Elemental analysis(calc. for C₇₇H₉₁O₁₀P₃=1269.48 g/mol): C, 73.07 (72.85); H, 7.25 (7.23);P, 7.37 (7.32) %. ³¹P NMR (CD₂Cl₂): δ 102.5-103.7 (1P), 118.5-119.8(1P), 135.6-136.3 (1P) ppm. EI-MS: m/e 1268 (38%, M⁺−H), 1085 (43%).

Compound 10 a) Chlorophosphite from 2-hydroxynicotinic acid,2-chloro-4H-[1,3,2]dioxaphosphinino[4,5-b]pyridin-4-one

A solution of 2-hydroxynicotinic acid (0.5 g, 3.594 mmol) andtriethylamine (1.5 ml, 10.783 mmol) in THF (20 ml) is admixed underagitation with PCl3 (0.494 g, 3.594 mmol), dissolved in THF (8 ml) andadded at −20° C. After stirring at room temperature overnight and at 70°C. for 2 h, the reaction solution is filtered and the solid material iswashed with THF (5 ml). The filtrate is concentrated to dryness in vacuoand the yellow residue is dried at 50° C./0.1 KPa for 1 h. Yield: 0.519g (2.550 mmol, 71%). The solid material has an NMR purity of 95 mol %and was used in the next step of the synthesis without furtherpurification.

¹H NMR (CD₂Cl₂): δ□ 7.37 (dd, 1H), 8.40 (dd, 1H), 8.53 (dd, 1H) ppm.

b) Conversion to Compound 10

A solution of 1 (1.859 g, 1.861 mmol) in toluene (22 ml) is admixed atroom temperature under agitation with triethylamine (0.82 ml, 5.869mmol) and then at 0° C. with a solution of2-chloro-4H-[1,3,2]dioxaphosphinino[4,5-b]pyridin-4-one (0.4544 g, 2.233mmol) in toluene (14 ml). The mixture is warmed to room temperature,stirred overnight and filtered and the filter cake is washed with THF(2×4 ml). The combined filtrates are concentrated to dryness in vacuoand dried at 50° C./1 mbar for 3 h. The residue is stirred with 50 ml ofhexane overnight. After filtering, the solvent is distilled off in vacuoand the solid substance obtained is dried at 70° C./0.1 KPa for 5 h.Yield: 2.00 g (1.715 mmol, 92%). Elemental analysis (calc. forC₆₄H₆₆O₁₄NP₃=1166.14 g/mol): C, 64.48 (65.92); H, 5.70 (5.70); P, 7.98(7.97); N, 1.36 (1.20); ¹H NMR (CD₂Cl₂): δ 0.77-1.62 (36H), 3.56-3.74(12H), 5.89-8.44 (18H) ppm. EI-MS: m/e 1165 (13%, M⁺).

Compound 11

A solution of 22 (2.135 g, 1.941 mmol) in toluene (18 ml) is admixed atroom temperature under agitation with triethylamine (1.08 ml, 7.765mmol) and then at 0° C. with solid 1,8,9-anthracene-triol (0.439 g,1.941 mmol). The mixture is warmed to room temperature, stirredovernight and filtered, the solvent is removed in vacuo, and the residueis dried at 50° C./0.1 KPa for 5 h. Yield: 2.35 g (1.875 mmol, 96%).Elemental analysis (calc. for C₇₂H₇₁O₁₄P₃=1253.26 g/mol): C, 69.18(69.00); H, 5.86 (5.71); P, 7.34 (7.42) %. □¹H NMR (CD₂Cl₂): δ 0.77-1.46(36H), 3.41-3.71 (12H); 5.78-8.42 (22H), 12.06+12.76 (1H) ppm. EI-MS:m/e 1253 (2%, M⁺), 999 (100%).

Compound 12

A solution of 22 (1.082 g, 0.983 mmol) in toluene (10 ml) is admixed atroom temperature under agitation with triethylamine (0.55 ml, 3.934mmol) and then at 0° C. with solid 1,9-anthracenediol (0.207 g, 0.983mmol). The mixture is warmed to room temperature, stirred overnight andfiltered, the solvent is removed in vacuo, and the residue is dried at60° C./0.1 KPa for 4 h. The residue is purified by column chromatography(dichloromethane/hexane=1:1, R_(f)=0.27). Yield: 0.931 g (0.752 mmol,76%). Elemental analysis (calc. for C₇₂H₇₁O₁₃P₃=1237.26 g/mol): C, 69.77(69.90); H, 5.93 (5.78); P, 7.52 (7.51) %. □¹H NMR (CD₂Cl₂): δ 0.90-1.65□(36H), 3.61-3.91 (12H), 6.05-8.28 (23H) ppm. EI-MS: m/e 1238 (11%, M⁺),982 (43%), 579 (100%).

Compound 13

A solution of 11 (0.674 g, 0.537 mmol) in THF (4 ml) is admixed with asolution of hexamethyldisilazane (0.433 g, 2.689 mmol) in THF (8 ml)added dropwise, refluxed for 14 h and then concentrated to dryness. Theresidue is purified by column chromatography (eluenthexane/dichloromethane, 1:2, R_(f)=0.47). Yield: 0.482 g (0.364 mmol,68%). Elemental analysis (calc. for C₇₅H₇₉O₁₄P₃Si=1325.44 g/mol): C,67.59 (67.96); H, 6.09 (6.01); P, 6.89 (7.01); Si, 2.15 (2.12) %. ¹H NMR(CD₂Cl₂): δ 0.00-1.53 (45H), 3.20-3.75 (12H), 5.88-7.91 (22H) ppm.According to NMR spectroscopy, there are two diastereomeric products.ESI/TOF-HRMS: m/e 1325.45076 (M+H)⁺.

Compound 14

A solution of 23 (0.47 g, 0.390 mmol) and triethylamine (0.158 g, 1.561mmol) in toluene (5 ml) is admixed at 0° C. with solid1,8,9-anthracenetriol (0.088 g, 0.390 mmol). After stirring at roomtemperature overnight and at 70° C. for 2 h, the reaction solution isfiltered and the filtrate is concentrated to dryness in vacuo. Theresidue is purified by column chromatography (eluenthexane/dichloromethane, 2:1, R_(f)=0.4). Yield: 0.270 g (0.199 mmol,51%). Elemental analysis (calc. for C₈₄H₉₅O₁₀P₃=1357.58 g/mol): C, 74.30(74.32); H, 6.89 (7.05); P, 6.80 (6.85) %. ³¹P NMR (CD₂Cl₂): δ 103.2 (s,br), 104.2 (s, br), 104.4 (d, J_(PP)=10 Hz), 104.7 (s, br), 105.3 (s),106.4 (d, J_(PP)=10 Hz), 135.6 (s, br), 136.0 (s, br), 136.3 (s, br)ppm. According to NMR spectroscopy, there are three diastereomericproducts. ESI/TOF-HRMS: m/e 1357.62109 (M+H)⁺.

Compound 15

A solution of 3 (1.479 g, 1.455 mmol) and triethylamine (0.462 g, 4.568mmol) in toluene (20 ml) is admixed under agitation with a solution of2-chloro-4H-benzo[d][1,3,2]dioxaphosphinin-4-one (0.338 g, 1.673 mmol)in toluene (10 ml) at 0° C. After stirring at room temperatureovernight, the reaction solution is filtered and the filtrate isconcentrated to dryness in vacuo. The solid material obtained is driedat 50° C./0.1 KPa for 2 h and purified by recrystallizing fromacetonitrile. Yield: 1.133 g (0.958 mmol, 66%). Elemental analysis(calc. for C₆₁H₅₅O₁₀P₃Cl₄=1182.82 g/mol): C, 61.49 (61.94); H, 4.71(4.69); P, 7.85 (7.86) %. ¹H NMR (CD₂Cl₂): δ 0.82-1.46 (36H), 5.98-7.94(19 H_(arom)). According to NMR spectroscopy, there are sixdiastereomeric products. EI-MS: m/e 1182 (10%, M⁺).

Compound 16

A solution of 5 (0.999 g, 1 mmol) in toluene (12 ml) is admixed at roomtemperature under agitation with triethylamine (0.53 ml, 3.781 mmol) andthen at 0° C. with a solution of2-chloro-4H-benzo[d][1,3,2]dioxaphosphinin-4-one (0.203 g, 1 mmol) intoluene (4 ml). The reaction mixture is warmed to room temperature,stirred overnight and filtered. The filtrate is concentrated to drynessin vacuo, and the residue is dried at 40° C./0.1 KPa for 3 h and thenpurified by column chromatography (mobile phase hexane/dichloromethane,1:10, R_(f)=0.8). Yield: 1.107 g (0.950 mmol, 95%) Elemental analysis(calc. for C₆₅H₆₇O₁₄P₃=1165.15 g/mol): C, 67.35 (67.01); H, 5.80 (5.80);P, 8.01 (7.97) %. ESI-TOF HRMS (MeOH/0.1% HCOOH in H₂O 90:10) m/e1187.3633 (100%, M+Na)⁺.

Compound 17

To a solution of 1 (1.487 g, 1.489 mmol) and triethylamine (0.472 g,4.673 mmol) in toluene (17 ml) is added at 0° C. a solution of2-chloronaphtho[1,8-de][1,3,2]dioxaphosphinine (0.333 g, 1.489 mmol) intoluene (10 ml). After stirring at room temperature overnight, thereaction solution is filtered and the filtrate is concentrated todryness in vacuo. The solid material obtained is dried at 50° C./0.1 KPafor 2 h and recrystallized from acetonitrile (20 ml). Yield: 1.087 g(0.915 mmol, 61%). Elemental analysis (calc. for C₆₈H₆₉O₁₃P₃=1187.20g/mol): C, 68.67 (68.80); H, 5.90 (5.86); P, 7.83 (7.83) %. ¹H NMR(CD₂Cl₂): δ 1.00-1.63 (36H), 3.67-3.89 (12H), 6.02-8.02 (21H) ppm.EI-MS: m/e 1187 (20%, M⁺).

Compound 18

A solution of 1 (1.289 g, 1.289 mmol) in THF (12 ml) is admixed at −20°C. with an equimolar amount of n-BuLi in hexane (5 ml). Warming to roomtemperature is followed by stirring overnight and the mixture thusobtained is added at 0° C. to a solution of4,8-di-tert-butyl-6-chloro-2,10-dimethoxydibenzo[d,f][1,3,2]dioxa-phosphepine (0.545 g, 1.289 mmol) in THF (9 ml). Themixture is stirred at room temperature for 16 h and concentrated todryness in vacuo. The residue is stirred with toluene (12 ml) andfiltered, the filtrate is concentrated in vacuo and the residue is driedat 50° C./0.1 KPa for 3 h. ³¹P NMR (CD₂Cl₂): δ 102.8, 104.4, 106.6,109.6, 132.8, 134.4, 134.9, 136.9, 143.4 ppm.

Compound 19

a) Dimeric anthracenetriol by the method of: W. Geiger, Chem. Ber. 1974,107, 2976-2984.b) A suspension of anthracenetriol dimer (0.298 g, 0.6615 mmol) intoluene (2 ml) is admixed under agitation with triethylamine (0.29 ml,2.083 mmol) and then at 0° C. with a solution of4,8-di-tert-butyl-6-chloro-2,10-dimethoxydibenzo[d,f][1,3,2]dioxaphosphepine(1.119 g, 2.646 mmol) in toluene (10 ml), which is added dropwise. Themixture is stirred at room temperature overnight and at 70° C. for anadditional 6 h and filtered, the frit residue is washed with warmtoluene (5 ml) and the filtrates are concentrated to dryness in vacuo.Crude yield: 0.589 g (0.295 mmol, 44%). Stirring with acetonitrile (10ml), filtration, taking up of the frit residue in THF (5 ml) andaddition of acetonitrile (8 ml) are followed by crystallization. Thesolid material obtained is dried in vacuo. Elemental analysis (calc. forC₁₁₆H₁₂₆O₂₂P₄=1996.15 g/mol): C, 69.48 (69.80); H, 6.20 (6.36); P, 6.15(6.21) %. ¹H NMR (CD₂Cl₂): δ □ 1.35 (36H), 1.37 (36H), 3.37 (2H), 3.66(12H), 3.71 (12H), 5.60-6.93 (28H) ppm. ESI/TOF-HRMS: m/e 1995.7740(M⁺), EI-MS: m/e 998 (47%, homolysis product under excitation conditionsof EI-MS).Compound 20 (2× toluene)

A suspension of anthracenetriol dimer (0.400 g, 0.888 mmol) in toluene(28 ml) is admixed under agitation with triethylamine (0.4 ml, 2.892mmol) and then at −20° C. with a solution of 21,4,8-di-tert-butyl-6-(3,3′-di-tert-butyl-2′-(dichlorophosphinooxy)-5,5′-dimethoxybiphenyl-2-yloxy)-2,10-dimethoxydibenzo[d,f][1,3,2]dioxaphosphepine,(1.488 g, 1.776 mmol) in toluene (32 ml), added dropwise. The mixture isstirred at room temperature overnight and at 70° C. for an additional 2h and filtered, the filtrate is concentrated to dryness in vacuo and theresidue is dried at 50° C./0.1 KPa for 2.5 h. The solid materialobtained is stirred with acetonitrile (40 ml) overnight and filtered andthe filter residue is dried at 50° C./0.1 KPa for 4 h. Yield: 0.757 g(0.379 mmol, 43%). Elemental analysis (calc. for C₁₃₀H₁₄₂O₂₂P₄=2180.28g/mol): C, 70.91 (71.61); H, 6.37 (6.56); P, 5.56 (5.68) %. ¹H NMR(CD₂Cl₂): δ □0.74-1.45 (72H), 3.6-3.7 (24H), 6.2-9.1 (28H), 11.56-12.13(2H) ppm. ESI/TOF-HRMS: m/e 1996.7820 (M+H toluene₂)⁺

Compound 214,8-Di-tert-butyl-6-(3,3′-di-tert-butyl-2′-(dichlorophosphinooxy)-5,5′-dimethoxybiphenyl-2-yloxy)-2,10-dimethoxy-dibenzo[d,f][1,3,2]dioxaphosphepine

A solution of3,3′-di-tert-butyl-2′-(4,8-di-tert-butyl-2,10-dimethoxydibenzo[d,f][1,3,2]dioxaphosphepin-6-yloxy)-5,5′-dimethoxybiphenyl-2-ol(prepared by the method of D. Selent, D. Hess, K.- D. Wiese, D. Röttger,C. Kunze, A. Borner, Angew. Chem. 2001, 113, 1739) (11.37 g, 15.26 mmol)and triethylamine (3.09 g, 30.54 mmol) in toluene (133 ml) is admixedunder agitation with PCl₃ (2.51 g, 18.31 mmol), dissolved in toluene (17ml), at 0° C. After stirring at room temperature overnight and at 85° C.for 3.5 h, the reaction solution is filtered and the filtrate isconcentrated to dryness in vacuo. The residue is dried at 60° C./1 mbarfor 2.5 h, then dissolved in hexane (125 ml) and stored at 5° C.overnight. The crystalline material obtained is filtered, and thefiltrate residue is washed with cold hexane (20 ml) and dried. Yield:8.97 g (10.6 mmol, 69%). ¹H NMR (CD₂Cl₂): δ□ 1.17 (s, 9H), 1.30 (s, 9H),1.51 (s, 9H), 1.56 (s, 9H), 3.81 (s, 3H), 3.85 (2s, 6H), 3.86 (3H), 6.71(d, 1H), 6.74 (d, 1H), 6.81 (d, 1H), 6.83 (d, 1H), 6.95 (d, 1H), 7.04(d, 1H), 7.06 (d, 1H), 7.09 (d, 1H) ppm. EI-MS, m/e 809 (2%, [M−Cl]⁺);727 (100%).

Compound 22

A solution of 1 (1.0 g, 1.001 mmol) in toluene (6 ml) is admixed at roomtemperature under agitation with triethylamine (0.28 ml, 2.002 mmol) andthen at 0° C. with a solution of phosphorus trichloride (0.152 g, 1.1mmol) in toluene (2 ml). After warming to room temperature, stirringovernight and filtration, the solvent is removed in vacuo. The residueis stirred with 10 ml of hexane for 16 h and filtered, the filterresidue is dried at 50° C./0.1 KPa for 3 h. Yield: 0.86 g (0.781 mmol,78%). ³¹P NMR (CD₂Cl₂): δ 102.8 (s), 103.5 (s), 103.9 (d), 134.9 (s,br), 198.7 (s), 199.3 (s), 203.3 (d) ppm (diastereomer mixture). Thesummed intensities in the particular expectation range correspond to a1:1:1 ratio for the 3 P atoms.

Compound 23

A solution of 2 (0.6 g, 0.545 mmol) and triethylamine (0.109 g, 1.087mmol) in toluene (9 ml) was admixed under agitation with a solution ofPCl3 (0.070 g, 0.516 mmol) in toluene (2 ml) added dropwise at 0° C.After stirring at room temperature overnight, the reaction solution isfiltered and the filtrate is concentrated to dryness in vacuo. Theresidue is dried at 50° C./0.1 KPa for 3 h and used in the next step ofthe synthesis without further purification. ³¹P NMR (CD₂Cl₂): δ□100.9(dd, J_(PP)=71 Hz; 4 Hz), 102.9 (s, br), 103.4 (dd, J_(PP)=3 Hz; 3 Hz),135.2 (s, br), 135.7 (dd, J_(PP)=8 Hz, 4 Hz), 135.9 (s, br), 199.9 (dd,J_(PP)=71 Hz, 8 Hz), 203.1 (d, J_(PP)=3 Hz), 203.2 (s, br).

Compound 24

Compound 24 was prepared similarly to 21 by reacting the correspondingphosphite phenol (D. Selent, D. Hess, K.- D. Wiese, D. Röttger, C.Kunze, A. Borner, Angew. Chem. 2001, 113, 1739) with PCl₃. The crudeproduct was washed with hexane and dried at 50° C./0.1 KPa for 2 h toobtain spectroscopically pure material. Yield: 72%. ¹H NMR (CD₂Cl₂): δ1.11 (s, 9H), 1.27 (s, 9H), 1.36 (s, 9H), 1.38 (s, 9H), 1.40 (s, 9H),1.41 (s, 9H), 1.52 (s, 9H), 1.58 (s, 9H), 7.14 (d, J_(HH)=2.5 Hz, 1H),7.16 (d, J_(HH)=2.5 Hz, 1H), 7.24 (d, J_(HH)=2.5 Hz, 1H), 7.31 (d,J_(HH)=2.5 Hz, 1H), 7.39 (d, J_(HH)=2.5 Hz, 1H), 7.50 (d, J_(HH)=2.5 Hz,1H), 7.53 (d, J_(HH)=2.5 Hz, 1H), 7.55 (d, J_(HH)=2.5 Hz, 1H) ppm.

NMR-Spectroscopic Testing for Stability

Ligand 17 and the bidentate comparative ligand BiPhePhos were eachdissolved in untreated toluene-D₈, transferred into an NMR vial andsealed. The ligand content was tracked by NMR spectroscopy for 32 days.

The results are shown in FIG. 1. Ligand 17 has a significantly higherstability than the comparative ligand BiPhePhos, as is clearly apparentin FIG. 1. In fact, the comparative ligand BiPhePhos is no longerNMR-detectable after day 32, while ligand 17 is measured at aconcentration of 60% relative to the initial value.

From this stability test of free ligand 17 and of free BiPhePhos ligand,the stability of a corresponding catalytically active composition, as ofthe rhodium complex derivatives formed therefrom for example, isdirectly derivable. For a hydroformylation process operated with thiscatalytically active composition, it means that the on-stream time of acatalytically active composition based on ligand 17 is distinctlyextended and thus economically optimized. This is accomplished withoutneed for a further stabilizing component, for example the addition ofsterically bulky amine derivatives—disclosed in EP 2280920. Thesubsequent catalyst tests with different olefins or differentolefin-containing hydrocarbonaceous streams demonstrate this technicalteaching in detail.

Verification Structure of Tridentate Character

A rhodium complex of ligand 17 was prepared and isolated in x-raysuitable quality. The structure derived from the x-rayograph is asfollows:

The data obtained verify the 3-fold coordination of rhodium on P^(III).Hence the solution contains a potentially higher P^(III) concentrationon the transition metal with the consequence that:

-   -   rhodium is kept in solution, and thus in the form of the        catalytically active composition, better and    -   the literature-described clustering of rhodium is suppressed.

Ligand dissociation and clustering are less favoured than in bidentatesystems, thus providing the catalytically active composition with alonger on-stream time.

Verification Structure of Tridentate Character as Binuclear Structure

A rhodium complex of ligand 17 was prepared and isolated in x-raysuitable quality. The structure derived from the x-rayograph is asfollows:

The data obtained additionally verify the structure of a binuclearrhodium complex in the catalytically active composition. Thestabilization of a second rhodium atom per complex in the catalyticallyactive composition is thus proven and thereby additionally prevents anyclustering, i.e. loss of rhodium.

Of the initially outlined requirements for novel ligands, the points:

-   -   improved resistance to inherent catalyst poisons and also    -   suppression of rhodium clustering by multiple coordination with        tridentate ligands and forming binuclear complexes are satisfied        by providing the compounds of the present invention and by their        use as ligands.

The ability of compounds according to the present invention to effectisomerizing hydroformylation when used as ligands in a catalyticallyactive composition is disclosed in the following catalysis tests onolefins and also olefin-containing mixtures:

Operating Prescription for Catalysis Tests

The hydroformylation was carried out in a 200 ml autoclave equipped witha pressure regulator to keep a constant pressure, a gas flowmeter, asparging stirrer and a pressure pipette. To minimize any influence dueto moisture and oxygen, not only the solvents (Tol=toluene, PC=propylenecarbonate, THF=tetrahydrofuran) but also the substrates were dried. Forthe tests, the autoclave was filled under argon with solutions ofrhodium in the form of [(acac)Rh(COD)](acac=acetylacetonate anion;COD=1,5-cyclooctadiene) as catalyst precursor in toluene. Then, thecorresponding amount of toluene-dissolved phosphite compound, generallyfrom 2 to 5 ligand equivalents per rhodium, was admixed. The mass oftoluene introduced in each case was determined. Starting weight ofolefins: 1-octene (10.62 g, 94.64 mmol), n-octene (10.70 g, 95.35 mmol),2-pentene (2.81 g, 40.0 mmol, characterized in table below with “(P)”,or 9.75 g, 139.00 mmol. 1-Butene, 2-butene and isobutene were added insimilar fashion. The autoclave was heated to the particular reportedtemperatures at an overall gas pressure (synthesis gas: H₂ (99.999%):CO₂ (99.997%)=1:1) of a) 4.2 MPa for a final pressure of 5.0 MPa; b) 1.2MPa for the final pressure of 2.0 MPa; and c) 0.7 MPa for a finalpressure of 1.0 MPa; under agitation (1500 rpm). On reaching thereaction temperature, the synthesis gas pressure was raised to a) 4.85MPa for a final pressure of 5.0 MPa, b) 1.95 MPa for a final pressure of2.0 MPa and c) 0.95 MPa for a final pressure of 1.0 MPa and theparticular olefin or olefin-containing mixture reported in the table wasinjected at about 0.3 MPa overpressure setting in the pressure pipette.The reaction was carried on for 4 h at a constant pressure ofrespectively 5.0, 2.0 and 1.0 MPa. After the reaction time had passed,the autoclave was cooled down to room temperature, let down underagitation and purged with argon. A 1 ml sample of each reaction mixturewas taken immediately the stirrer was switched off, diluted with 5 ml ofpentane and analyzed by gas chromatography: HP 5890 Series II plus,PONA, 50 m×0.2 mm×0.5 μm. Quantitative determination of aldehyde andresidual olefin was against the solvent toluene as internal standard.

Catalysis tests with compounds 6 to 17.

Yield=yield based on starting olefin or olefin-containing mixture

Sel. (%)=n-selectivity (%)

1-Octene

Li- P T (° t [Rh] Sol- Yield Sel. gand (MPa) C.) (h) (ppm) L/Rh vent (%)(%) 7 5.0 100 4 40 1 Tol 85 95.8 7 5.0 100 4 40 2 Tol 86 95.5 9 5.0 1004 40 2 Tol 86 94.9 9 5.0 100 4 40 2 PC 84 95.0 10 5.0 100 4 40 2 Tol 8795.6 15 5.0 100 4 40 2 Tol 86 96.1 11 5.0 100 4 40 2 Tol 90 97.2 16 5.0100 4 40 2 Tol 90 91.0 17 5.0 100 4 40 4 Tol 91 89.5

All ligands used are tridentate and perform in the reaction with good tooutstanding yields and also respectively outstanding n-selectivities.The respective catalytically active compositions need only minimalligand excesses for these performances, as the L/Rh ratio in the tableshows.

n-Octenes

(octene isomer mixture of 1-octene: 3.3%, cis+trans-2-octene: 48.5%,cis+trans-3-octene: 29.2%, cis+trans-4-octene: 16.4%, structurallyisomeric octenes: 2.6%)

Li- P T (° t [Rh] Sol- Yield Sel. gand (MPa) C.) (h) (ppm) L/Rh vent (%)(%) 7 2.0 120 4 100 1 Tol 68 84.2 7 2.0 120 4 100 2 Tol 79 85.5 7 2.0120 4 100 10 Tol 74 85.6 8 2.0 120 4 100 2 PC 85 87.1 17 2.0 120 4 100 2Tol 76 84.4

All ligands used are tridentate and perform in the reaction with good tooutstanding yields and also respectively outstanding n-selectivities.The respective catalytically active compositions need only minimalligand excesses for these performances, as the L/Rh ratio in the tableshows. Higher ligand excesses are unnecessary, as is illuminated by theexample of ligand 7 in the table.

2-Pentene (15 ml, 2.41 M)

(P) characterizes lower 2-pentene use (see above)

Li- P T (° t [Rh] Sol- Yield Sel. gand (MPa) C.) (h) (ppm) L/Rh vent (%)(%) 7 2.0 120 4 100 1 Tol 93 89.6 (P) 7 2.0 120 4 100 1 PC 87 91.6 (P) 72.0 120 4 100 2 Tol 95 90.2 (P) 7 2.0 120 4 100 2 PC 93 92.4 (P) 7 2.0120 4 100 2 PC 90 92.2 7 2.0 120 4 100 5 Tol 95 90.0 7 2.0 120 4 100 10Tol 95 90.4 (P) 7 2.0 120 4 100 2 Tol 94 89.7 7 2.0 120 4 120 1.7 Tol 9689.9 7 2.0 120 4 100 2/2 Tol 96 90.2 TINUVIN ® 7 2.0 100 4 100 2 PC 8991.7 7 2.0 100 4 100 2 Tol 91 90.5 7 2.0 120 4 100 2 Tol 94 89.7 8 2.0120 4 100 2 PC 95 92.7 8 2.0 120 4 100 5 PC 92 92.6 8 2.0 120 4 100 10PC 95 92.6 8 2.0 120 4 100 2 Tol 95 90.6 8 2.0 120 4 100 2 THF 94 91.0 81.0 120 4 100 2 PC 92 90.7 8 2.0 100 4 100 2 PC 93 92.0 8 2.0 110 4 1002 PC 94 92.4 10 2.0 120 4 100 2 PC 92 92.6 10 2.0 120 4 100 2 Tol 9590.2 10 2.0 120 4 100 5 Tol 95 90.2 10 2.0 100 4 100 2 PC 90 92.8 11 2.0120 4 100 2 Tol 95 93.8 (P) 11 2.0 120 4 100 2 Tol 96 93.9 11 2.0 120 4100 2 PC 93 94.3 (P) 11 2.0 120 4 100 1 Tol 91 93.4 (P) 11 2.0 120 4 1005 Tol 95 94.4 (P) 11 1.0 120 4 100 2 Tol 96 93.6 11 1.0 110 4 100 2 Tol91 94.1 11 2.0 120 4 100 2 PC 99 94.4 11 1.0 110 4 100 2 PC 94 95.1 111.0 100 4 100 2 PC 90 95.8 11 2.0 100 4 100 2 PC 87 93.9 12 2.0 120 4100 2 Tol 97 90.4 12 2.0 120 4 100 2 PC 97 91.9 12 1.0 100 4 100 2 PC 8794.2 13 2.0 120 4 100 2 PC 89 94.5 13 1.0 110 4 100 2 PC 84 95.6 13 1.0110 4 100 2 PC 91 95.4 14 2.0 120 4 100 2 Tol 88 89.7 (P) 15 2.0 120 4100 2 PC 95 92.6 15 2.0 120 4 100 2 Tol 91 90.1 6 2.0 120 4 100 2 Tol 6588.6 17 2.0 100 4 100 2 Tol 87 89.6 17 2.0 120 4 100 2 Tol 93 90.8 172.0 120 4 100 5 Tol 97 90.2 17 2.0 120 4 100 2 PC 97 91.8

The extensive series of catalysis tests with 2-pentene has 2 specialfeatures compared with the other series of tests:

-   -   a bidentate compound is used in ligand 6 and a distinct        reduction in yield compared with the other ligands used is        recorded;    -   the tridentate ligand 7 is reacted in one test together with a        sterically bulky amine derivative branded as        TINUVIN®=di-4-(2,2,6,6-tetramethyl)piperidinyl sebacate—without        better results being achieved in respect of yield and        n-selectivity.

C4 Olefins

Li- Sub- P T (° t [Rh] L/ Sol- Yield Sel. gand strate (MPa) C.) (h)(ppm) Rh vent (%) (%) 17 2- 2.0 120 5 40 3.9 Tol- 93.8 90.2 Butene uene17 1- 2.0 120 5 37 6.0 Tol- 82.2 87.8 Butene uene 17 Iso- 2.0 100 5 386.0 Tol- 64.6 100 butene uene

1. A compound, comprising a structure of formula (I):

wherein the compound comprises at least two O—P^(III) bonds, which areoptionally formed with the same P^(III) or from different P^(III)s; whenthe compound comprises two structures of formula (I), a first structureof formula (I) and a second structure of formula (I) are connected toeach other by a C10-C10′ carbon bond or via a unit of:—X¹-G¹-X²— where X¹ is connected to a P^(III) of the first structure andX² to a P^(III) of the second structure, G¹ is a linear or branched,aliphatic or aromatic or heteroaromatic or fused aromatic or fusedaromatic-heteroaromatic hydrocarbon group with any desired furthersubstitution, X¹, and X² are each independently selected from the groupconsisting of O, NY¹, and CY²Y³, where Y¹, Y², and Y³ are eachindependently selected from the group consisting of hydrogen, asubstituted or unsubstituted aliphatic group, and a substituted orunsubstituted aromatic hydrocarbon group, with two or more of Y¹ to Y³optionally linked to each other covalently; R¹, R², R³, R⁴, R⁵, R⁶, andR⁷ are selected from the group consisting of hydrogen, a substituted orunsubstituted, linear or branched, aliphatic or aromatic hydrocarbongroup; F, Cl, Br, I, —OR⁸, —C(O)R⁹, —CO₂R¹⁰, —CO₂M¹, —SR¹, —SOR¹²,—SO₂R¹³, —SO₃R¹⁴, —SO₃M², —NR¹⁵R¹⁶; and —OR¹⁷, where R⁸, R⁹, R¹⁰, R¹⁰,R¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶ are selected from the group consisting ofhydrogen, a substituted or unsubstituted, linear or branched, aliphaticor aromatic or heteroaromatic or fused aromatic or fusedaromatic-heteroaromatic hydrocarbon group, R¹⁷ is selected from thegroup consisting of hydrogen, an unsubstituted or substituted, linear orbranched, aliphatic or aromatic hydrocarbon group; two or more of R¹ toR¹⁷ are optionally linked to each other covalently; and M¹ and M² areeach independently selected from the group consisting of an alkalimetal, an alkaline earth metal, ammonium, and phosphonium.
 2. Thecompound according to claim 1, further comprising: a structure offormula (II):

wherein W is selected from the group consisting of hydrogen; analiphatic, aromatic, heteroaromatic, fused aromatic, fusedaromatic-heteroaromatic hydrocarbon group with any desired furthersubstitution; a P^(III)(G²)(G³) group:

where G² and G³ are each independently selected from the groupconsisting of hydrogen; a linear or branched, aliphatic or aromatic orheteroaromatic or fused aromatic or fused aromatic-heteroaromatichydrocarbon group with any desired further substitution; F, Cl, Br, I,—OR¹⁸, —C(O)R¹⁹, —CO₂R²⁰, —CO₂M¹, —SR²¹, —SOR²², —SO₂R²³, —SO₃R²⁴,—SO₃M², —NR²⁵R²⁶; and —OR²⁷, where R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴,R²⁵, and R²⁶ are selected from the group consisting of hydrogen, asubstituted or unsubstituted, linear or branched, aliphatic or aromatichydrocarbon group, R²⁷ is selected from the group consisting ofhydrogen, a substituted or unsubstituted, linear or branched, aliphaticor aromatic hydrocarbon group; F, Cl, Br, and I; and M¹ and M² are eachindependently selected from the group consisting of an alkali metal, analkaline earth metal, ammonium, and phosphonium, and G² and G³ areoptionally linked to each other covalently; SiR²⁸R²⁹R³⁰, where R²⁸, R²⁹,R³⁰ are each independently hydrogen; a linear or branched, aliphatic oraromatic or heteroaromatic or fused aromatic or fusedaromatic-heteroaromatic hydrocarbon group with any desired furthersubstitution and R²⁸ and R²⁹ are optionally linked to each othercovalently.
 3. The compound according to either claim 1, furthercomprising a structure of formula (III):

wherein Z is G⁴ or an X¹-G¹-X² unit, where G⁴ is selected from the groupconsisting of hydrogen; a linear or branched, aliphatic or aromatic orheteroaromatic or fused aromatic or fused aromatic-heteroaromatichydrocarbon group with any desired further substitution, F, Cl, Br, I,—OR³¹, —C(O)R³², —CO₂R³³, —CO₂M¹, —SR³⁴, —SOR³⁵, —SO₂R³⁶, —SO₃R³⁷,—SO₃M², —NR³⁸R³⁹, and —OR⁴⁰; where R¹, R³², R³³, R³⁴, R³⁵, R³⁶, R³⁷,R³⁸, R³⁹, and R⁴⁰ are selected from the group consisting of hydrogen, asubstituted or unsubstituted, linear or branched, aliphatic or aromatichydrocarbon group; and M¹ and M² are each independently selected fromthe group consisting of an alkali metal, an alkaline earth metal,ammonium, and phosphonium.
 4. The compound according to claim 2, furthercomprising: a structure of formula (IV):

wherein G⁵ and G⁶ are each independently selected from the groupconsisting of hydrogen; a linear or branched, aliphatic or aromatic orheteroaromatic or fused aromatic or fused aromatic-heteroaromatichydrocarbon group with any desired further substitution; F, Cl, Br, I,—OR⁴¹, —C(O)R⁴², —CO₂R⁴³, —CO₂M¹, —SR⁴⁴, —SOR⁴⁵, —SO₂R⁴⁶, —SO₃R⁴⁷,SO₃M², —NR⁴⁸R⁴⁹ and —OR⁵⁰; where R⁴¹, R⁴², R⁴⁴, R⁴⁴, R⁴⁵, R⁴⁶, R⁴⁷, R⁴⁸,R⁴⁹ and R⁵⁰ are selected from the group consisting of hydrogen, asubstituted or unsubstituted, linear or branched, aliphatic or aromatichydrocarbon group; and M¹ and M² are each independently selected fromthe group consisting of an alkali metal, an alkaline earth metal,ammonium, and phosphonium, and G⁵ and G⁶ are optionally linked to eachother covalently.
 5. The compound according to claim 2, wherein W is aP^(III)(G²)(G³) group.
 6. The compound according to claim 2, wherein G²,and G³ are —OR¹⁸.
 7. The compound according to claim 4, wherein G⁵, andG⁶ are —OR⁴¹.
 8. The compound according to claim 1, wherein X¹, and X²are O.
 9. The compound according to claim 1, wherein G¹ comprises abisarylene group having any desired further substitution.
 10. Thecompound according to claim 1, wherein G¹ comprises a structure offormula (V):

where R⁵¹, R⁵², R⁵³, R⁵⁴, R⁵⁵, R⁵⁶, R⁵⁷, and R⁵⁸ are each independentlyhydrogen; a linear or branched, aliphatic or aromatic or heteroaromaticor fused aromatic or fused aromatic-heteroaromatic hydrocarbon groupwith any desired further substitution; F, Cl, Br, I; —OR⁵⁹, —COR⁶⁰,—CO₂R⁶¹, —CO₂M¹, —SR⁶², —SOR⁶³, —SO₂R⁶⁴, —SO₃R⁶⁵, —SO₃M², —NR⁶⁶R⁶⁷,N═CR⁶⁸R⁶⁹; or —OR⁶⁸, two or more of R⁵¹ to R⁵⁸ are optionally linked toeach other covalently; R⁵⁹, R⁶⁰, R⁶¹, R⁶², R⁶³, R⁶⁴, R⁶⁵, R⁶⁶, R⁶⁷ andR⁶⁸ are selected from the group consisting of hydrogen, a substituted orunsubstituted, linear or branched, aliphatic or aromatic hydrocarbongroup; M¹ and M² are each independently selected from the groupconsisting of an alkali metal, an alkaline earth metal, ammonium, andphosphonium, and a and b are attachment points to X¹ and X².
 11. Thecompound according to claim 1, wherein G² and G³ are linked to eachother covalently.
 12. The compound according to claim 2, wherein G²-G³comprises a structure of formula (VI):

where R⁶⁹, R⁷⁰, R⁷¹, R⁷², R⁷³, R⁷⁴, R⁷⁵, and R⁷⁶ are each independentlyhydrogen; a linear or branched, aliphatic or aromatic or heteroaromaticor fused aromatic or fused aromatic-heteroaromatic hydrocarbon groupwith any desired further substitution; F, Cl, Br, I; —OR⁷⁷, —COR⁷⁸,—CO₂R⁷⁹, —CO₂M¹, —SR⁸⁰, —SOR⁸¹, —SO₂R⁸², —SO₃R⁸³, —SO₃M², —NR⁸⁴R⁸⁵,N═CR⁸⁶R⁸⁷; or —OR⁸⁶, two or more of R⁶⁹ to R⁷⁶ are optionally linked toeach other covalently; R⁷⁷, R⁷⁸, R⁷⁹, R⁸⁰, R⁸¹, R⁸², R⁸³, R⁸⁴, R⁸⁵ andR⁸⁶ are selected from the group consisting of hydrogen, a substituted orunsubstituted, linear or branched, aliphatic or aromatic hydrocarbongroup; and M¹ and M² are each independently selected from the groupconsisting of an alkali metal, an alkaline earth metal, ammonium, andphosphonium.
 13. The compound according to claim 4, wherein G⁵ and G⁶are linked to each other covalently.
 14. The compound according to claim4, wherein G⁵-G⁶ comprises a structure of formula (VII):

where R⁸⁷, R⁸⁸, R⁸⁹, R⁹⁰, R⁹¹, R⁹², R⁹³, and R⁹⁴ are each independentlyhydrogen; a linear or branched, aliphatic or aromatic or heteroaromaticor fused aromatic or fused aromatic-heteroaromatic hydrocarbon groupwith any desired further substitution; F, Cl, Br, I; —OR⁹⁵, —COR⁹⁶,—CO₂R⁹⁷, —CO₂M¹, —SR⁹⁸, —SOR⁹⁹, —SO₂R¹⁰⁰, —SO₃R¹⁰¹, —SO₃M², —NR¹⁰²R¹⁰³,N═CR¹⁰⁴R¹⁰⁵; or —OR¹⁰⁴, two or more of R⁸⁶ to R⁹³ are optionally linkedto each other covalently; R⁹⁵, R⁹⁶, R⁹⁷, R⁹⁸, R⁹⁹, R¹⁰⁰, R¹⁰¹, R¹⁰²,R¹⁰³ and R¹⁰⁴ are selected from the group consisting of hydrogen, asubstituted or unsubstituted, linear or branched, aliphatic or aromatichydrocarbon group; and M¹ and M² are each independently selected fromthe group consisting of an alkali metal, an alkaline earth metal,ammonium, and phosphonium.
 15. The compound according to claim 4,wherein the P^(III)(G²)(G³) group corresponds in terms of structuralformula to the P^(III)(G⁵)(G⁶) group.
 16. A complex, comprising: thecompound according to claim 1, and a central metal atom, wherein thecompound is coordinated onto the central metal atom via at least oneP^(III).
 17. The complex according to claim 16, wherein the centralmetal atom is one of groups 8 to 10 metals.
 18. The complex according toclaim 17, wherein the central metal atom is rhodium.
 19. A composition,comprising: a central metal atom, and at least two compounds accordingto claim 1, wherein a first compound is not coordinated onto a centralmetal atom, and a second compound is coordinated onto the central metalatom via at least one P^(III). 20-21. (canceled)
 22. A multiphasicreaction mixture, comprising: an olefinically unsaturated hydrocarbonmixture, a gas mixture comprising carbon monoxide and hydrogen,aldehydes, and the composition according to claim 19 as a catalyticallyactive composition.
 23. A process for hydroformylation of anolefinically unsaturated hydrocarbon mixture to aldehydes, comprising:adding the catalytically active composition according to claim 19 intothe mixture; introducing a mixture comprising carbon monoxide andhydrogen, thereby obtaining a reaction mixture; heating the reactionmixture to a temperature of from 80 to 120° C.; building a pressure offrom 1.0 to 6.4 MPa; and removing the olefinically unsaturatedhydrocarbon mixture.
 24. The process according to claim 23, furthercomprising: recycling unconverted olefinically unsaturated hydrocarbonmixture.
 25. The process according to claim 23, further comprising:removing and recycling the catalytically active composition.
 26. Theprocess according to claim 23, further comprising: removing andrecycling unconverted gas mixture comprising carbon monoxide andhydrogen.